Housefly, horn fly, and mosquito repellents and apparatus useful in testing efficacy of same

ABSTRACT

Described is a method of repelling insects by utilizing as active insect repellent ingredient 2,4-dimethyl-4-phenyl-1-butanol or  alpha -terpinyl methyl ether (ORANGE FLOWER ETHER).

This is a divisional of application Ser. No. 08/130,398, filed Oct. 1,1993, which, in turn, is a continuation-in-part of Ser. No. 07/982,374filed on Nov. 25, 1992, now U.S. Pat. No. 5,281,621 issued on Jan. 25,1994; which, in turn, is a continuation-in-part of Ser. No. 07/789,695filed on Nov. 8, 1991, now abandoned; which, in turn, is a divisional ofSer. No. 07/643,206 filed on Jan. 18, 1991, now U.S. Pat No. 5,126,369issued on Jun. 30, 1992.

BACKGROUND OF THE INVENTION

Our invention relates to the use of PAMPLEFLEUR® having the structure:##STR1## (2,4-dimethyl-4-phenyl-1-butanol), VIOLIFF™ which contains amajor quantity of the compound having the structure: ##STR2##(methyl-4-cyclooctenyl carbonate), ORANGE FLOWER ETHER having thestructure: ##STR3## (1-methyl-4(2'-methoxy-2'-propyl)-l-cyclohexene,INDISAN™ containing a major proportion of the compound having thestructure: ##STR4## and diethyl phthalate having the structure: ##STR5##for repelling blood feeding arthropods, species of mosquitoes, houseflies and horn flies, as well as apparatus for determining repellencyand attractancy of semiochemicals such as the aforementioned materialsagainst and for such blood feeding arthropods.

Ethers, esters and alcohols are known for repelling insects and theprior art contains many references pertaining to same. Thus, the use ofthe compound having the structure: ##STR6## as a repellent againstvarious insect species is disclosed in Application for U.S. Pat. Ser.No. 08/007,287 filed on Jan. 21, 1993, assigned to the assignees of theinstant invention.

Nothing in the prior art however sets forth the unexpected, unobviousand advantageous insect repellency properties of the alcohols, ethersand esters of our invention so useful in repelling the species ofinsects set forth herein.

The prior art is replet with references showing various traps forinsects including U.S. Pat. No. 4,759,228 issued on Jul. 26, 1988 andincluding the above-mentioned Application for U.S. Pat. Ser. No.08/007,287 filed on Jan. 21, 1993. Other prior art showing such insecttraps is:

Griffiths and Bowman, Acarology VI, Volume 2, published by Ellis HorwoodLimited 15.5, "Sampling techniques for burrow-dwelling ticks inreference to potential African swine fever virsu vectors", (Butler, etal).

Garcia, R., (1962), Ann. Entomol.Soc.Amer., 55 605-606.

Garcia, R., (1965), Amer.J.Trop.Med.Hyg., 14 1090-1093.

Hair, J. A., Hoch, A. L., Barker, R. W., Semtner, P. J., (1972), J. Med.Entomol., 99 153-155.

Holscher, K. H. Gearhart, H. L., Barker, R. W. (1980)Ann.Entomol.Soc.Amer., 73 288-292.

Koch, H. G. & McNew, R. W., (1981), Ann.Entomol.Soc. Amer., 74, 498-500.

Nothing in the prior art sets forth the trap of our invention.

SUMMARY OF THE INVENTION

Our invention is directed to a semiochemical field trap for bloodfeeding arthropods, which has the capability of causing determination ofrepellency and attractancy of semiochemicals against and for bloodfeeding arthropods. The field trap comprises:

(1) An upright vertically disposed first hollow outer housing havingsubstantially rigid arthropod-impermeable first side walls, an upperarthropod-impermeable horizontal surface substantially entirelycontiguous with said first side walls, and a substantially entirely openbottom having a substantially horizontal plane substantiallyperpendicular to the vertical axis of said first hollow outer housing;(for example, such a first hollow outer housing can be a hollow frustumof a cone or a pyramid fabricated from such a material as aluminum);

(2) Located along an axis substantially perpendicular to the horizontalplane of the substantially entirely open bottom of said first outerhousing, substantially parallel to the vertical axis of said firsthollow housing and within said first hollow housing, a second innerhollow housing having a hollow interior, opposite open upper first andlower second ends, vertically-disposed rigid arthropod-impermeable sidewalls, and a longitudinal dimension extending between the two ends, saidupper first end being at a substantial distance below said uppersubstantially horizontal surface of said first outer housing (forexample, the second inner hollow housing can be an open-ended cylinderfabricated of impermeable tin or aluminum);

(3) Extending outwardly from the substantially vertically disposed sidewalls of the second inner hollow housing to the side walls of the firsthollow outer housing at an angle of from about -5° up to about -40° ,measured downwardly from the substantially horizontal plane of the openbottom of the first hollow outer housing, substantially rigid ribcomponents (for example, fabricated from steel, stainless steel or iron)which enable the fixed positioning of the inner hollow housing withrespect to the positioning of and within said outer hollow housing (thepreferred angle being about -10°);

(4) Completely encompassingly traversing in a substantially tightfitting manner the area between (i) the first side walls of said firstouter hollow housing and (ii) the second side walls of said second innerhollow housing along the directional vectors of said rib components andin a curvilinear plane below and substantially contiguous to said ribcomponents, a continuous substantially macroporous mesh substance havingsuch a mesh size as to be impenetrable by arthropods sought to beentrapped, but pervious to gas and liquid and, in addition, radiationtransmittable, and capable of supporting a matrix article containingsustainably releasable semiochemical (for example, nylon mesh having amesh size in lines per inch of from about 10 up to about 200);

(5) Optionally, at least one semiochemical-containing matrix comprisinga porous containment agent (e.g., polyethylene, polypropylene, apolyamid, a polyurethane or the like) containing in the intersticesthereof at least one semiochemical sustainably releasable thereform,(e.g., one or more of the ketone, alcohol or schiff base of ourinvention) located on the upper surface of said macroporous meshsubstance (e.g., nylon mesh);

(6) A substantially vertically disposed drive shaft supported for rotarymotion about its axis, extending from below and into the hollow interiorof the second inner hollow housing along the longitudinal dimensionthereof;

(7) Motor means connected to a first lower end of the drive shaft forrotating the drive shaft about its axis;

(8) Air flow creation means (e.g., a propeller) attached to a secondupper end of the drive shaft, being of such a design whereby therotation of the drive shaft directly causes the rotation of the air flowcreation means and induces the flow of air from beneath the second innerhollow housing upwardly into the three space within the first outerhollow housing upwardly into the three space within the first outerhollow housing (e.g., the hollow frustum of a cone) between the outerside wall of the second inner hollow housing (e.g., the open endedcylinder) and the inner side wall of the first outer hollow housing(e.g., the hollow frustum of the cone);

(9) Radiation emission means (e.g., an infrared light source or a brightgreen light source) for emission of radiation of a specific wave lengthor of a range of wave lengths cutwardly from the apparatus located inthe vicinity of the lower portion of the second inner hollow housingbelow the location of the rib components:

(10) Radiation pulsing means connected to said radiation emission meanscausing said radiation to have a frequency minicking insect wing beatand/or insect visual sensing frequencies;

(11) Power supply means (e.g., flashlight batteries) associated with thetrap causing the radiation emission means to generate radiation andenergizing the radiation pulsing means and the motor means;

whereby arthropods (e.g., the listed mosquitoes, horn flies and houseflies) in the vicinity of the trap are attracted by the pulsed radiationto a location so close to the trap that in the event that an attractingsemiochemical in the matrix is detected by the arthropods, thearthropods will enter the air stream created by the air flow creationmeans and be carried into the 3-space within the first hollow outerhousing between the outer side wall of the second inner hollow housingand the inner side wall of the first outer hollow housing. As statedabove, it is optional in the operation of the trap to include thesemiochemical-containing matrix.

The trap of our invention is intended to test not only semiochemicals(e.g., insect attractants and repellents) and the attractancy orrepellency of various types of radiation such as infrared light, but mayalso be used to test the attractancy or air as well as gases. Thus, thetrap of our invention may also include:

(11) A carbon dioxide gas supply means for supplying gaseous carbondioxide to the proximity of the lower portion of the second inner hollowhousing below the location of the rib components simultaneously with theoperation of the power supply means. The carbon dioxide itself has theability to attract various types of insects. It is our intention tocover the trap including and not including the carbon dioxide gas supplymeans.

Preferably, there should be approximately 0.25 inches -0.50 inchesclearance between the top of the second inner housing (e.g., cylinder)and the bottom of the upper arthropod-impermeable horizontal surface ofthe first hollow outer housing. Furthermore, the air flow creation means(e.g., propeller) should preferably protrude 0.125 inches -0.25 inchesfrom the bottom of the second inner hollow housing (e.g., open-endedmetal cylinder).

It is preferable when using the radiation emission means, to useinfrared light. Control experiments are preferably run using carbondioxide with the use of infrared radiation lights and without the use ofinfrared radiation lights. However, experiments using the trap may alsobe carried out with other lights such as bright green lights. In bothcases, the radiation emission means utilize the circuit, preferably, ofFIG. 5 of U.S. Pat. No. 5,205,065 issued on Apr. 27, 1993, thespecification for which is incorporated by reference herein. Othercircuits are used when using laser diodes instead of light emittingdiodes. An example of the green light being used is one manufactured bythe Marktech International Corporation of Menands, N.Y., Catalog PartNo. MT300-CUG (T-1.75 water clear ultra-bright green light emittingdiode lamp) When using infrared radiation means, it is preferable toutilize a gallium arsenide infrared light emitting diode such as ModelMTE 1080 gallium arsenide emitter manufactured by Marktech of 120Broadway, Menands, N.Y. 12204. When using a laser diode, laser diodessuch as those marketed under Catalog Nos. P451 or P452 by the DIGI-KEY®Corporation of 701 Brooks Avenue South, P.O. Box 677, Thief River Falls,Minn. 56701-0677 are useful and operable.

The radiation pulsing means is intended herein to be a flicker fusionfrequency generator to present a frequency of from about 50 up to about400 cycles per second (Herz). Such frequencies are intended to mimicblood feeding arthropod wing beat frequencies and visual sensingfrequencies. The radiation pulsing means is intended to cause the firingof, for example, radiation emitting diodes having a range of from about400 up to about 1000 nm (nanometers).

The radiation pulsing means can be in the form of a direct radiationstroblight such as that illustrated in FIG. 17 of application for U.S.patent Ser. No. 08/007287 filed on Feb. 21, 1993, the specification forwhich is incorporated by reference herein or it can be in the form of anoff-apparatus stroblight unit which causes radiation pulsing to beconveyed through fiber optic strands as set forth, for example, in FIG.19 of application for U.S. patent Ser. No. 08/007287 filed on Feb. 21,1993, the specification for which is incorporated by reference herein.

In any event, radiation pulsing means which can be used in the practiceof our invention are set forth in the following publications:

(i) published Canadian Patent Application 2,040,615 published on Oct.17, 1992 (title: "Cel-Alert" An Easy To-Use Emergency Strobe-Light RoadSafety Device";

(ii) the Stroboscope/Tachometer marketed by the Edmund ScientificCompany of Barrington, N.J.;

(iii) the "Realistic Wide Angle Strobe Light" Catalog No. 42-3009Amarketed by the Radio Shack Division of Tandy Corporation of Ft. Worth,Tex.;

(iv) the Enerlite Personal Strobe, Catalog No. 61-2506 marketed by theRadio Shack Division of Tandy Corporation of Ft. Worth, Tex. Other lightemitting diodes that are useful in the practice of our invention are,for example, those set forth in Canadian Published Patent Application2,065,577 published on Oct. 17, 1992 entitled "Encapsulated LightEmitting Diode And Method For Encapsulation".

When preparing the semiochemical matrix which is preferably a block, 10microliters of test material, e.g., at least one of the alcohols, estersor ether used in our invention are soaked into a 9 mm×9 mm×9 mm block.The carbon dioxide supply source is most conveniently dry ice placed ina "zippered" bag (with a tygon tubing outlet). The dry ice is placed ina zippered bag and the bag is then placed in an insulated ice chest.Preferably between 4 and 5 kilograms of dry ice is used, preferably inthe form of pellets or blocks.

On placing the trap in the test area, the motor means is engaged withthe power supply means, preferably simultaneously with the engagement ofthe radiation means and radiation pulsing means with the power supplymeans. Thus, at the instant that the trap is commenced to be in use, theair flow or carbon dioxide flow creation means (e.g., the propeller)begins its rotation simultaneously with the radiation means andradiation pulsing means being energized and with the motor means beingenergized. Thus, arthropods, e.g., mosquitoes, house flies, and hornflies as set forth, supra, in the vicinity of the trap are attracted bythe pulsing radiation to a location so close to the trap that in theevent that an attracting semiochemical in the matrix is detected by thearthropods, the arthropods will enter the air or carbon dioxide streamcreated by the air flow creation means, e.g., propeller and be carriedinto the 3-space within the first hollow outer housing between the outerside wall of the second inner hollow housing and the inner side wall ofthe first outer hollow housing. Once within the trap the arthropods willnot escape in view of the fact that they are in the vicinity of thecarbon dioxide being emitted by the carbon dioxide supply source andthey are in the vicinity of the pulsing radiation emitted by the pulsingradiation emission means and are attracted thereto. Furthermore, therotation of the air flow creation means prevents the arthropods fromleaving the 3-space within the first hollow outer housing where they aretrapped. The traps are usually run for a period of from about 36 hoursup to about 40 hours. They are set up in usually four rows of four,approximately 60 feet apart.

Preferably, the mesh size of the nylon used for the continuoussubstantially macroporous mesh substance of the trap should range fromabout 10 up to about 200 lines per inch and thus, for example, may be20/6 T-66 textured nylon or 70/32 polyester (e.g., a polymer of phthalicanhydride and ethylene glycol).

More specifically, our invention is directed to a method for repellingat least one of the insect species:

(a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Cullseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.;

(j) Lutzomyia spp.;

(k) Aedes spp.;

(l) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(p) Simuliidae spp.;

(q) Psorohora ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.)

for a finite period of time from a three dimensional space comprisingthe step of exposing said three dimensional space inhabited by:

(a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Culiseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.;

(j) Lutzomyia spp.;

(k) Aedes spp.;

(l) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(p) Simuliidae spp.;

(q) Psoroforia ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.)

to a composition of matter which is at least one of the esters, alcoholsor ether-containing composition of matter, to wit:

(1) PAMPLEFLEUR® having the structure: ##STR7##(2,4-dimethyl-4-phenyl-l-butanol) prepared according to Example III,columns 20, 21 and 22 of U.S. Pat. No. 4,610,812 issued on Sep. 9, 1986,the specification for which is incorporated by reference herein;

(2) VIOLIFF™ containing a major amount of the compound having thestructure: ##STR8## and a minor amount of the compound having thestructure: ##STR9## prepared according to the process of Example II(bulked distillation Fractions 7-14) of U.S. Pat. No. 4,452,730 issuedon Jun. 5, 1984, the specification for which is incorporated byreference herein; produced according to the process of

(i) reacting 1,5-cyclooctadiene with formic acid to form a mixture offormates containing a major quantity of 4-cyclooctenyl formates; and

(ii) reacting the resulting mixture of formates with dimethyl carbonatein the presence of an alkali metal methoxide to form a mixture of methylcarbonate containing a major quantity of 4-cyclooctenyl methylcarbonate;

(3) ORANGE FLOWER ETHER having the structure: ##STR10##(1-methyl-4(2'-methoxy-2'-propyl)-l-cyclohexene; (4) A mixture ofcompounds containing a major proportion of the compound having thestructure: ##STR11## (for example, INDISAN™ or SANDIFF™ (trademark ofInternational Flavors & Fragrances Inc.)) prepared by:

(i) reacting catechol or quiacol with camphene in the presence of aFriedel-Crafts Catalyst to form an alkylation product;

(ii) treating the alkylation product with hydrogen to form a dioxyintermediate; and then

(iii) treating the dioxy intermediate with hydrogen to form ameta-(isocamphyl-5) cyclohexanyl containing mixture (for example,prepared according to the process of Example XIII of U.S. Pat. No.4,014,944 issued on Mar. 29, 1977 the specification for which isincorporated by reference herein); and

(5) Diethyl phthalate having the structure: ##STR12##

Another aspect of our invention relates to the formation of the insectrepelling articles, that is, the articles containing at least one of thealcohols, esters and/or ether useful for the repelling of the insectspecies:

(a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Cullseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.; and/or

(j) Lutzomyia spp.;

(k) Aedes spp.;

(1) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(p) Simuliidae spp.;

(q) Psorophora ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.)

in combination with compatible polymers, e.g., high density polyethyleneor low density polyethylene. Thus, one aspect of our invention providesa process for forming semiochemical-containing polymeric particles suchas foam polymeric pellets which include a relatively high concentrationof at least one of the alcohols, esters and/or ether useful in ourinvention.

Thus, one aspect of our invention relates to the formation ofsemiochemical polymeric pellets by means of introduction into a singlescrew or twin screw extruder of, in series, a thermoplastic polymerfollowed by a semiochemical which is compatible with the thermoplasticpolymer, in turn (optionally) followed by introduction of a gaseousblowing agent or blowing agent which will produce a gas which is inertto the polymer and to the alcohols, esters and ether semiochemicalpreviously introduced into the extruder.

The advantages of using a foamed polymeric particle are multiple, towit: improved handling, greater retention of the semiochemical, that is,at least one of the alcohols, esters or ether when not in use; greaterlength of time during which the release of the semiochemical from thepolymer is at "steady state" or "zero order".

The nature of the extruder utilized in the process of our invention toform the polymeric semiochemical-containing polymer particles of ourinvention may be either single screw or double screw. Thus, the types ofextruder that can be used are disclosed at pages 246-257 and 332-349 ofthe Modern Plastics Encyclopedia, 1982-1983, published by theMcGraw-Hill Published Company. More specifically, examples of extruderswhich are usable in carrying out one of the processes of our invention(with modification for introduction of the semiochemical) downstreamfrom the introduction of the polymer and with further modification thatthe gaseous blowing agent is introduced still further downstream fromthe point of introduction of the semiochemical, e.g., at least one ofthe alcohols, esters and/or ether of our invention are as follows:

1. The Welex "Super Twinch" 3.5" extruder manufactured by WelexIncorporated, 850 Jolly Road, Blue Bell, Pa. 19422;

2. Krauss-Maffei twin screw extruder manufactured by the Krauss-MaffeiCorporation/Extruder Division, 3629 West 30th Street South, Wichita,Kans. 67277;

3. Modified Sterling Model 4000 and 5000 series extruder manufactured bySterling Extruder Corporation of 901 Durham Avenue, South Plainfield,N.J.;

4. CRT ("Counter-Rotating Tangential") Twin Screw Extruder manufacturedby Welding Engineers, Inc.1 of King of Prussia, Pa. 19406;

5. The Leistritz Twin Screw Dispersion Compounder manufactured by theAmerican Leistritz Extruder Corporation of 198 U.S. Route 206 South,Somerville, N.J. 08876;

6. The ZSK Twin Screw Co-Rotating Extruder manufactued by the Werner &Pfleiderer Corporation of 6763 East Crescent Avenue, Ramsey, N.J. 07446;

7. The Farrel Extruder manufactured by Farrel Connecticut Division,Emhart Machinery Group, Ansonia, Conn. 06401;

8. The MpC/V Baker Perkins Twin Screw Extruder manufactured by the BakerPerkins Inc. Chemical Machinery Division of Saginaw, Mich. 48601; and

9. The Berstorff single screw, twin screw, or foam extrusion equipmentmanufactured by Berstorff Corporation, P.O. Box 240357, 8200-AArrowridge Boulevard, Charlotte, N.C. 28224.

In producing the semiochemical (e.g., alcohols, esters and/or ether)polymer particles of our invention, various polymers may be utilized,for example, low density polyethylene, high density polyethylene,polypropylene, the co-polymer of ethylene and vinyl acetate, andpolyvinyl chloride. More specifically, the polymers used in the practiceof our invention may be co-polymers of ethylene and a polar vinylmonomer selected from (a) vinyl acetate; (b) ethyl acrylate; (c) methylacrylate; (d) butyl acrylate and (e) acrylic acid including thehydrolyzed copolymer of ethylene and vinyl acetate. Prefered copolymersare polyethylene-vinyl acetate with about 9% to 60% vinyl acetate andethylene/ethyl acrylate with about 6% to 18% ethyl acrylate.

Resins of the type disclosed for use as co-polymers are commerciallyavailable in the molding powder form. For example, ethylene vinylacetate co-polymers are marketed by the E. I. duPont de Nemours Companyunder the tradename "ELYAX®" and by the Arco Polymer Division under thetrademark "DYLAND®" and by the Exxon Corporation of Linden, N.J. underthe trademark "DEXXON®" . Ethylene/ethyl acrylate co-polymers aremarketed by Union Carbide Corporation under the tradename "EEA RESINS®".

The polymer is added to the single screw or twin screw extruder at afeed rate in the range of from about 80 up to about 300 pounds per hourwhile maintaining the temperature of the screw extuder between about160° C. and about 240° C. If the polymer or co-polymer powder is addedto the extruder at a reference "barrel segment", then at least one ofthe alcohols, esters or ether useful in our invention is added to theextruder under pressure downstream from the addition point of thepolymer at one or more of "barrel segments" S-2, S-3, S-4, S-5, S-6,S-7, S-8 or S-9 (referring to FIG. 6 briefly described, infra, anddescribed in detail, infra).

The concentration of at least one of the alcohols, esters or ether inthe semiochemical-containing resin can vary from small but effectiveamounts on the order of about 1% of the weight of the resin body up toabout 45% by weight of the resin body. In general it is preferred to usebetween about 5% up to about 30% based on the weight of the resin bodyof at least one of the esters, alcohols or ethers useful in ourinvention. This is an optimum amount balancing the proportion of atleast one of the esters, alcohols or ether useful in our inventionagainst the time period over which the article omits at least one of theesters, alcohols or ether useful in our invention and against thetendency of at least one of the alcohols, esters or ether to "oil out".This "oiling out" is specifically avoided as a result of the use of thefoaming agent discussed, infra.

Various polymers are useful in the practice of our invention. Specificexamples of polymers useful in the practice of our invention are asfollows:

(a) DYLAN® brand of low density polyethylene DYLAN® is a trademark ownedby the Atlantic Richfield Company of Los Angeles, Calif.;

(b) DYLITE® of expandable polystyrene compositions. DYLITE® is atrademark of the Atlantic Richfield Company of Los Angeles, Calif.;

(c) SUPER DYLAN® is a high density polyethylene. SUPER DYLAN® is atrademark of the Atlantic Richfield Company of Los Angeles, Calif.;

(d) Blended polyethylene and carbon black as specifically taught in U.S.Pat. No. 4,369,267 issued on Jan. 18, 1983, the specification for whichis incorporated by reference herein;

(e) Polystyrene as disclosed in U.S. Pat. No. 4,369,227 issued on Jan.18, 1983, the specification for which is incorporated by referenceherein;

(f) Polyene/alpha-olefin as exemplified and disclosed in U.S. Pat. No.4,369,291, the specification for which is incorporated by referenceherein;

(g) Poly-alpha-olefins as exemplified in Canadian Letters Patent No.1,137,069 issued on Dec. 7, 1982;

(h) Polymeric compositions as disclosed in Canadian Letters Patent No.1,137,068 issued on Dec. 7, 1982;

(i) Poly-alpha-olefins disclosed in Canadian Letters Patent No.1,137,067;

(j) Polyolefins described in Canadian Letters Patent No. 1,137,066;

(k) Polyethylene oxides as disclosed in Canadian Letters Patent No.1,137,065 issued on Dec. 7, 1982;

(l) Olefin polymers and co-polymers as disclosed in Canadian LettersPatent No. 1,139,737; Canadian Patent No. 1,139,737 was issued on Jan.18, 1983;

(m) Polyolefins disclosed in Canadian Letters Patent No. 1,139,738;Canadian Patent No. 1,139,738 was issued on Jan. 18, 1983;

(n) Chlorinated PYC as disclosed in Polymer 1982, 23 (7, Suppl.), 1051-6abstracted at Chem. Abstracts Volume 97:145570y, 1982;

(o) Polyepsilon caprolactone co-polymers made by means of alcoholinitiated polymerization as disclosed in J.Polym.Sci.Polym.Chem.Ed.,1982, 20(2), pages 319-26, abstracted at Chem. Abstracts Volume96:123625x, 1982;

(p) Styrene acrylonitrile co-polymers as disclosed in Diss. Abstracts,Int. B, 1982, 42(8), 3346 and abstracted at Chem. Abstracts Volume96:143750n (1982);

(q) Co-polymers of epsilon caprolactone with 1,4-butane diol asdisclosed at Kauch. Rezine, 1982, (2), 8-9, abstracted at Chem.Abstracts Volume 96:182506g (1982);

(r) Polyesters as disclosed in U.S. Pat. No. 4,326,010, thespecification for which is incorporated by reference herein;

(s) Chlorinated polyethylene as disclosed by Belorgey, et al,J.Polym.Sci.Polym., Phys.Ed, 1982, 20(2), 191-203;

(t) Plasticized polyepsilon caprolactone co-polymers containing dimethylphthalate plasticizers as set forth in Japanese Patent No. J81/147844,abstracted at Chem. Abstracts Volume 96:69984y (1982);

(u) Maleic anhydride modified adducts of polyepsilon caprolactonepolyols and ethylenically unsaturated monomer as disclosed in U.S. Pat.No. 4,137,279 issued on Jan. 30, 1979, the specification for which isincorporated by reference herein;

(v) Polyurethane polymers having lactone backbones as disclosed in U.S.Pat. No. 4,156,067 issued on May 22, 1979, the disclosure of which isincorporated by reference herein;

(w) Polyurethane polyether resins wherein the resin is obtained byreacting a polyfunctional lactone with a long chain polyalkylene dioland a urethane precursor as disclosed in U.S. Pat. No. 4,355,550 issuedon Mar. 10, 1981, the disclosure of which is incorporated by referenceherein; and

(x) Resins having polyurethane backbones as disclosed in U.S. Pat. No.3,975,350 issued on Aug. 17, 1976, the specification for which isincorporated by reference herein.

Downstream from the addition point of at least one of the esters,alcohols or ether, optionally, the gaseous or liquid containing blowingagent may be added (e.g., at barrel segments S-5, S-6, S-7, S-8, S-9 orS-10 of FIG. 6) using the polymer addition barrel segment as a referencebarrel segmen "S-1". Examples of gaseous blowing agents are carbondioxide, nitrogen, mixtures of nitrogen and carbon dioxide inproportions of from 1 up to 99% by volume nitrogen and 99 down to 1% byvolume carbon dioxide, helium, mixtures of helium and nitrogen, mixturesof helium and carbon dioxide and other gases which are inert at thetemperature and pressure of the polymer at the time of the extrusionoperation. This gas containing oxygen or other reactive gases, e.g.,hydrogen, should be avoided. The pressure of the gas blowing agent beingadded to the extruder at the point of addition may vary from about 80 upto about 150 psig. Higher pressures may be used without adverselyaffecting the usefulness of the foamed ester, alcohol orether-containing particle.

The feed rate range of the of the ester, alcohol or ether may be betweenabout 0.5% up to about 45% by weight of the polymer.

The die of the extruder may create rod, sheet, film or ribbon. Theresulting product may then, if desired, be pelletized to form alcohol,ester or ether (e.g., the ORANGE FLOWER ETHER having the structure:##STR13## -containing polymer particles or the ribbon may be used"as-is" as an alcohol, ester or ether containing polymeric article ofmanufacture itself.

In addition to the optional gaseous blowing agents (which arenecessarily "inert" gases), blowing agents may be added at the samepoint on the extruder which will create gaseous voids in the alcohol,ester or ether-containing polymer articles of our invention and these"blowing agents" are well known to one having ordinary skill in the art.

Examples of such non-gaseous containing materials which yield gases onadmixture with the polymer in the extruder but which are still inert tothe insect repellent are as follows:

(i) Under high pressure, ethylene, methane, propane, butane, propylene,methyl chloride, methyl bromide, vinyl chloride and methylene dichlorideas more specifically described in U.S. Pat. No. 2,387,730, thespecification for which is incorporated hereby by reference herein;

(ii) Ordinarily liquid material such as n-pentane, isopentane,cyclopentane, hexane and petroleum ether fractions or halogenhydrocarbons such as CFC₃, CF₂ Cl₂, Ch₃ Cl, CH₂ Cl₂ separately or inadmixture with one another as set forth in U.S. Pat. No. 3,758,425,column 4, lines 1-5, the specification for which is incorporated herebyby reference herein;

(iii) Dichlorotetrafluoroethane, tetramethylmethane,monochlorodifluoromethane, dichlorodifluoromethane, anddichlorotetrafluoroethane as specifically described in U.S. Pat. Nos.2,948,664 and 2,948,665 issued on Aug. 9, 1960,the specification forwhich is incorporated hereby by reference; and

(iv) Azo bis(formamide); diazoaminobenzene; N,N'-dinitrosopentamethylenetetramine; N,N'-dimethyl-N,N'-dinitrosoterephthalamide;p,p'-oxy-bis(benzene sulfonyl semicarbazide); azobis-(isobutyronitrile); p,p'-oxybis(benzene sulfonyl hydrazide);p,p'-diphenyl-bis (sulfonyl hydrazide); benzene-sulfonyl hydrazide;m-benzene-bis(sulfonyl hydrazide) as more specifically described in U.S.Pat. No. 3,298,975 issued on Jan. 17, 1967, the specification for whichis incorporated hereby by reference herein.

The resulting extruded (and if desired, pelletized) material may thenbe, for example, be injection molded to form a useful article. Suchinjection molding can be carried out in accordance with the procedure asset forth in U.S. Pat. No. 3,268,636 issued on Aug. 23, 1966, thespecification for which is incorporated hereby by reference herein.

In addition, our invention relates to candle body materials which on useare both insect repellent and perfuming and which contain of at leastone of the esters alcohols and/or ether of our invention (e.g., thePAMPLEFLEUR® having the structure: ##STR14## in order to repel at leastone of the insect species: (a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Culiseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.;

(j) Lutzomyia spp.;

(k) Aedes spp.;

(1) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(p) Simuliidae spp.;

(q) Psorohora ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.)

The insect repellent-perfume compositions which form part of the candlebody materials are within the following specifications:

(I) from 5% up to 100% by weight of an efficacious perfume/ insectrepellent composition consisting essentially of at least one of thealcohols, esters and/or ether useful in our invention, e.g., a mixtureof PAMPLEFLEUR® having the structure: ##STR15## and VIOLIFF™ having amajor proportion of the compound having the structure: ##STR16## and(II) from 0% up to 95% of a standard perfuming substance (notnecessarily insect repellent) which may be one or a combination of thefollowing materials:

the methyl ester of 2,5-dihydroxy-4-5-dimethyl benzoic acid;

dihydro myrcenol;

oakmoss absolute;

benzyl acetate;

geraniol;

isobornyl acetate;

citronelly acetate;

para-t-butyl phenyl isovaleraldehyde;

benzyl salicylate;

hexyl cinnamic aldehyde;

geranonitrile;

patchouli oil;

alpha-terpineol;

tetrahydromuguol;

phenyl ethyl alcohol;

cedrenal;

cinnamyl acetate;

benzyl benzoate;

L-Citronellal;

nerol;

geranyl formate;

geranyl acetate;

eugenol;

alpha Farnesene;

beta Farnesene;

citral;

n-Nonanal;

n-Octanal; and

trans, trans delta-damascone.

The foregoing formulae may require a solubilizing agent, e.g., themethyl ester of dihydroabietic acid (commerical name: HERCOLYN D®,benzyl benzoate, isopropyl myristate and/or C₁₂ -C₁₄ isoparaffinhydrocarbons.

The candle base composition can be standard paraffin wax, or it can betransparent or pastel shaded as more particularly described in U.S. Pat.No. 3,615,289 issued on Oct. 26, 1971 (the disclosure of which isincorporated by reference herein) and wherein the candle body comprisesas the basic components a mixture of:

(i) a thermoplastic polyamide resin formed from linoleic acidpolymerized with a polyamine compound;

(ii) an alkanol amide or alkanol amine; and

(iii) a stearic acid compound.

The weight ratio of the candle body: ester, alcohol or ether (e.g.,ORANGE FLOWER ETHER having the structure: ##STR17## perfumant substanceof our invention may vary from about 0.8% up to about 10% with a rangeof from about 0.8% up to about 2.0% being preferred when no non-insectrepelling perfume oil is used in conjunction with the alcohol, esterand/or ether composition of matter useful in our invention; and with arange of from about 1.5% up to about 10% by weight of the overallcomposition being preferred when a non-insect repelling perfume oil isused in conjunction with the ester, alcohol and/or ether useful in ourinvention.

Specifically, the polyamide may be a "VERSAMID®" resin which is athermoplastic condensation product of polymerized linoleic acid withvarious polyamine compounds such as ethylene diamine, ethylene triamineand the like. Specific "VERSAMID®" compounds are "VERSAMID®" 900,"VERSAMID®"930, "VERSAMID®"940, "VERSAMID®"948, "VERSAMID®"950 and"VERSAMID®"1635. These compounds are products of the Henkel ChemicalCorporation of Minneapolis, Minn. and "VERSAMID®" is a trademark ofHenkel Chemical Corporation of Minneapolis, Minn.

Another substance required in the clear candle composition consists ofabout 20-55% by weight of an alkanol amine or alknaol amide prepared bythe reaction of a fatty acid ester and amine whereby the ester and theamine are in substantially equal proportions, for example, compoundssuch as Barlol 12C2 (manufactured by the Barrid Chemical Company) amonoalkyl diethanolamine have 8 to 18% carbon atoms in the alkyl chain.A third component of the clear plastic candle composition comprises oneor more stearic acid esters or a mixture of stearic acid esters andstearic acid. These esters include such compounds as isopropylisostearate, butyl stearate and hexadecyl stearate. These stearic acidcompounds serve as stabilizing agents which permit the readyincorporation of the insect repellent/perfumant compositions of ourinvention up to a level of approximately 5% (total proportion of perfumeoil-insect repellent composition). They are carriers for theperfumant/insect repellent and may be used in a proportion of between 1and 50% by weight of the composition although the preferable range isbetween 20% to 30%. In this connection it is possible to use up to about10% by weight of perfumant/ insect repellent if part of the formula isreplaced by the material "Nevex 100", a product which is acoumarin-indene copolymer resin of very little unsaturation,manufactured by the Neville Chemical Company.

Rather than being a crystalline paraffin wax the candle base of ourinvention may be an oil gel that has as its base a light mineral oil, aninexpensive natural oil or a combination of such oils which oil gel hasa non-greasy surface and feel and sufficient rigidity to beself-supporting at room temperature. Such a gel is disclosed in U.S.Pat. No. 3,645,705 issued on Feb. 29, 1972, the disclosure of which isincorporated by reference herein. Such compositions of matter include:

(a) from about 35% up to about 85% by weight of an oil which is normallyliquid at room temperature chosen from the group consisting of lightmineral oil and natural oils having iodine values substantially withinthe range of 40-135;

(b) from about 7% up to about 40% by weight of a long chain polyamidehaving a molecular weight substantially within the range of 6000-9000and a softening point substantially within the range of 18° C.-48° C.;and

(c) from about 7% to about 30% of an alcohol selected from the groupconsisting of 8 to 12 carbon primary alcohols.

Such composition may additionally include from about 1% up to about 15%of a methyl ester; up to about 5% by weight of stearic acid and up toabout 5% by weight of an oxidation inhibiting agent and up to about 5%by weight of an acid selected from the group consisting of dimer andtrimer acids.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cut-away perspective view of the semiochemical field trapfor blood feeding arthropods of our invention showing blood feedingarthropods inside the trap being attracted to semiochemical-containingmatrices comprising a porous containment agent containing in theinterstices thereof at least one semiochemical sustainably releaseabletherefrom.

FIG. 2 is a schematic diagram (blown up for illustration purposes)showing laboratory olfactometer apparatus in perspective view useful inascertaining the efficacy of the esters, alcohols and ether compositionof our invention useful as repellents for house flies (Musca domesticaL.(Diptera:Muscidae)) and mosquitoes (Aedes aegypti) indicating inschematic block flow diagram form the utilization of computer assistedefficacy measuring apparatus.

FIG. 2A is a detailed section of the apparatus of FIG. 2 showing aspecific landing site on which an insect lands if attracted by, forexample, an ester, alcohol or ether-containing composition useful in ourinvention (e.g., the ORANGE FLOWER ETHER having the structure: ##STR18##or does not land if repelled by the alcohol, ester or ether-containingcomposition useful in our invention.

FIG. 3A is a bar graph showing the attractancy of air versus therepellency of diethylphthalate using the apparatus of FIG. 2 with a meanone hour feeding contact. The number of feeding contacts for mosquitoes(Aedes aegypti) is shown on the "y" axis and the given treatment isshown on the "x" axis.

FIG. 3B is a bar graph similar to that of FIG. 3A except that thefeeding contact is a mean 2-6 hour contact.

FIG. 4A is a series of graphs depicting in three dimensions (in therectangular mode for the "x" and "y" axes) showing the repellency ofINDISAN™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of one hour with six intervals of 10 minuteseach. The results are tabulated in Table I, infra. This series of graphsis for the attractiveness or repellency against house flies (Muscadomestica L.(Diptera:Muscidae)).

FIG. 4B is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the repellency ofINDISAN™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of one hour with six intervals of 10 minuteseach. The results are tabulated in Table II, infra. This series ofgraphs is for the attractiveness or repellency as against horn flies(Haemotobia irritans (L.)).

FIG. 4C is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the repellency ofINDISAN™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of one hour with six intervals of 10 minuteseach. The results are tabulated in Table III, infra. This series ofgraphs is for the attractiveness or repellency as against mosquitoes(Aedes aegypti).

FIG. 4D is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the repellency ofINDISAN™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of twelve hours with six intervals of twohours each. The results are tabulated in Table IV, infra. This series ofgraphs is for the attractiveness or repellency as against mosquitoes(Aedes aegypti).

FIG. 4E is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the repellency ofINDISAN™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of one hour with six intervals of tenminutes each. The results are tabulated in Table V, infra. This seriesof graphs is for the attractiveness or repellency as against mosquitoes(Aedes aegypti).

FIG. 4F is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the repellency ofINDISAN™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of one hour with six intervals of tenminutes each. The results are tabulated in Table VI, infra. This seriesof graphs is for the attractiveness or repellency as against mosquitoes(Aedes aegypti).

FIG. 4G is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the repellency ofINDISAN™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of twelve hours with six intervals of twohours each. The results are tabulated in Table VII, infra. This seriesof graphs is for the attractiveness or repellency as against mosquitoes(Aedes aegypti).

FIG. 5A is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the relativerepellency of ORANGE FLOWER ETHER (having the structure: ##STR19##PAMPLEFLEUR® having the structure: ##STR20## and VIOLIFF™ having as itsmajor ingredient the compound having the structure: ##STR21## as well asthe attractiveness of air. The graphs are based on experiments run for atotal of one hour with six intervals of ten minutes each. The resultsare tabulated in Table VIII, infra. This series of graphs is for theattractiveness or repellency as against mosquitoes (Aedes aegypti).

FIG. 5B is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the relativerepellency of VIOLIFF™, geraniol coeur, PAMPLEFLEUR® and ORANGE FLOWERETHER as well as the attractiveness of air. The graphs are based onexperiments run for a total of one hour with six intervals of tenminutes each. The results are tabulated in Table IX, infra. This seriesof graphs is for the attractiveness or repellency as against mosquitoes(Aedes aegypti).

FIG. 5C is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the relativerepellency of VIOLIFF™, geraniol coeur, PAMPLEFLEUR® and ORANGE FLOWERETHER as well as the attractiveness of air. The graphs are based onexperiments run for a total of six hours with six intervals of one houreach. The results are tabulated in Table X, infra. This series of graphsis for the attractiveness or repellency as against mosquitoes (Aedesaegypti).

FIG. 5D is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the relativerepellency of ORANGE FLOWER ETHER, PAMPLEFLEUR®, geraniol coeur, andVIOLIFF™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of one hour with six intervals of tenminutes each. The results are tabulated in Table XI, infra. This seriesof graphs is for the attractiveness or repellency as against mosquitoes(Aedes aegypti).

FIG. 5E is a series of graphs depicted in three dimensions (in arectangular mode for the "x" and "y" axes) showing the relativerepellency of ORANGE FLOWER ETHER, PAMPLEFLEUR®, geraniol coeur, andVIOLIFF™ as well as the attractiveness of air. The graphs are based onexperiments run for a total of six hours with six intervals of one houreach. The results are tabulated in Table XII, infra. This series ofgraphs is for the attractiveness or repellency as against mosquitoes(Aedes aegypti).

FIG. 6 is a cut-away side elevation schematic diagram of a screwextruder during the compounding of a resin with insect repellents,including one or more of the esters, alcohols or ether useful in ourinvention while simultaneously adding foaming agent into the hollowportion of the barrel of the extruder and incorporates the pelletizingapparatus used in the pelletizing of the extruded foamed tow productproduced as a result of the extrusion operation.

FIG. 7 is a perspective view of an ellipsodially-shaped detergent tabletcontaining a solid core which includes fused foamed polymeric particleswhich contain insect repellents which can be one or more of the esters,alcohols or ether of our invention and, if desired, also containing anadditional polymer, e.g., polyethylene. The polymer particles may, ifdesired, also contain additional aromatizing agents.

FIG. 8 is the top view of the ellipsodially-shaped detergent tablet ofFIG. 7.

FIG. 9 is a cut-away front view of the ellipsodially-shaped detergenttablet of FIG. 7 in the direction of the arrows in FIG. 8.

FIG. 10 is a side view of the ellipsodially-shaped detergent tablet ofFIG. 8.

FIG. 11 is a perspective view of a rectangular parallelpiped-shapeddetergent tablet containing a rectangular parallelpiped-shaped corecomprising a major proportion of fused foamed polymeric particles whichcontain insect repellent, (e.g., one or more of the esters, alcohols orether useful in our invention), e.g., the compound having the structure:##STR22## and may or may not be aromatized and, if desired, anadditional polymer which may or may not contain insect repellentcompositions and which may or may not be aromatized.

FIG. 12 is the top view of the rectangular parallelpiped-shapeddetergent tablet of FIG. 11.

FIG. 13 is a cut-away front view of the rectangular parallelpiped-shapeddetergent tablet of FIG. 11 looking in the direction of the arrows inFIG. 12.

FIG. 14 is a perspective view of an ellipsodially-shaped detergenttablet containing a hollow insect repellent agent (and, if desired, anaromatizing agent)-containing core which includes fused foamed polymericparticles. The insect repellent and, if desired, the aroma impartingagent is in the solid polymer and not in the void of the plastic core.

FIG. 15 is a top view of the ellipsodially-shaped detergent tablet ofFIG. 14.

FIG. 16 is a front cut-away view of the ellipsodially-shaped detergenttablet of FIG. 14 looking in the direction of the arrows in FIG. 15, thecore thereof being hollow and either containing an insect repellentmaterial (and, if desired, an aroma imparting liquid) or, in thealternative, being a hollow core wherein the insect repellent material(and, if desired, the aroma imparting material) is in the solid fusedfoamed polymric particles which make up the core and wherein the voiddoes not contain anything.

FIG. 17 is a bar graph showing a comparison of the field trial tests ofrepellents for mosquitoes, to wit:

(a') Aedes aegypti;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian;

comparing the use of VIOLIFF™ and PAMPLEFLEUR® repellent against a 50:50mixture of air and CO₂. The "x" axis sets forth the mean number ofmosquitoes trapped and the "y" axis sets forth the particularcomposition used in the treatment. The data was obtained using theapparatus of FIG. 1 described briefly, supra, and described in detail,infra.

FIG. 18 is a bar garph showing a comparison of the field trial tests ofair versus INDISAN™ for mosquitoes, to wit:

(a') Aedes aegypti;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian.

The mean number of mosquitoes is set forth on the "y" axis and thecomposition used in the treatment is set forth on the "x" axis. The datawas obtained using the apparatus of FIG. 1.

FIG. 19 is a bar graph showing a comparison of the field trial testsusing the apparatus of FIG. 1 of the repellent, VIOLIFF™ versus theattractant, air. The mean number of mosquitoes, to wit:

(a') Aedes aegypti ;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian;

is set forth on the "y" axis and the composition used in the treatment,e.g., air or VIOLIFF™ is set forth on the "x" axis.

FIG. 20 is a bar graph showing a comparison of the field trial testsusing the apparatus of FIG. 1 of the repellents geraniol coeur andPAMPLEFLEUR® having the structure: ##STR23## versus the attractant, a50:50 mixture of air and CO₂. The mean number of the mosquitoes, to wit:

(a') Aedes aegypti;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian;

is set forth on the "y" axis and the treatment composition, e.g., the50:50 mixture of air and CO₂, is set forth on the "x" axis.

FIG. 21 is the GLC profile for the reaction product of Example Vcontaining the compounds having the structures: ##STR24##

FIG. 22 is the GLC profile for Fraction 13 of the distillation productof the reaction product of Example V containing the compounds having thestructures: ##STR25##

FIG. 23 is the NMR spectrum for Fraction 13 of the distillation productof the reaction product of Example V containing the compounds having thestructures: ##STR26##

FIG. 24 is the infrared spectrum for Fraction 13 of the distillationproduct of the reaction product of Example V containing the compoundshaving the structures: ##STR27##

FIG. 25 is the GLC profile for Fraction 7 of the distillation product ofthe reaction product of Example V containing the compound having thestructure: ##STR28## in major proportion and the compound having thestructure: ##STR29## in minor proportion.

FIG. 26 is the NMR spectrum for Fraction 7 of the distillation productof the reaction product of Example V containing the compound having thestructure: ##STR30## in major proportion and the compound having thestructure: ##STR31## in minor proportion ( Solvent: CFCl₃ ; fieldstrength: 100 MHz).

FIG. 27 is the infrared spectrum for Fraction 7 of the distillationproduct of the reaction product of Example V containing the compoundhaving the structure: ##STR32## in major proportion and the compoundhaving the structure: ##STR33## in minor proportion (ratio of compoundhaving the structure: ##STR34## to compound having the structure:##STR35## being 77:19).

FIG. 28 is the GLC profile for INDISAN™ containing a major proportion ofthe compound having the structure: ##STR36## prepared by the steps of:(i) reacting guiacol with camphene in the presence of a Friedel-Craftscatalyst to form an alkylation product;

(ii) treating the alkylation product with hydrogen to form a dioxyintermediate; and

(iii) treating the dioxy intermediate with hydrogen to form ameta-(isocamphyl-5)cyclohexanol-containing mixture.

FIG. 29 is the GLC profile of the reaction product of the second stageof the hydrogenation of Example VI containing a major proportion of thecompound having the structure: ##STR37## Example VI corresponds toExample XIII of U.S. Pat. No. 4,014,944 issued on Mar. 29, 1977, thespecification for which is incorporated hereby by reference herein.

DETAILED DESCRIPTION OF THE DRAWINGS

Referring to FIG. 1, a semiochemical field trap 100 for blood feedingarthropods 29 comprises:

(1) An upright vertically-disposed first hollow outer housing 28 havingsubstantially rigid arthropod-impermeable first side walls 28b, an upperarthropod-horizontal surface 28a substantially entirely contiguous withsaid first side walls 28b and a substantially entirely open bottom 28dhaving a substantially horizontal plane substantially perpendicular tothe vertical axis 28c of said first hollow outer housing 28;

(2) Located along an axis 28c substantially perpendicular to thehorizontal plane 28d of said substantially entirely open bottom of saidfirst outer housing 28, substantially parallel to the vertical axis 28cof said first hollow housing 28, and within said first hollow housing28, a second inner hollow housing 37, having a hollow interior, oppositeopen upper first and lower second ends, vertically-disposed rigid,arthropod-impenetrable side walls 37a, and a longitudinal dimensionextending between the two ends, said upper first end being at asubstantial distance below said upper substantially horizontal surace28a of said first outer housing 28;

(3) Extending outwardly from said substantially vertically disposed sidewalls 37a of said second inner hollow housing 37 to the side walls 28bof the first hollow outer housing 28, at an angle of from about -5° C.up to about -40° C., measured downwardly from the substantiallyhorizontal plane 28 of the open bottom of said first hollow outerhousing 28, substantially rigid rib components 27, which enabled thefixed positioning of said inner hollow housing 37 with respect to thepositioning of and within said outer hollow housing 28;

(4) Completely encompassingly traversing in a substantially tightfitting manner the area between (i) the first side walls 28b of saidfirst outer hollow housing 28, and (ii) the second side walls 38a ofsaid second inner hollow housing 37 along the directional vectors ofsaid rib components 27 and in a curvilinear plane below andsubstantially contiguous to said rib components 27, a continuoussubstantially macroporous mesh substance 24, having such a mesh size asto be impenetrable by arthropods 29 sought to be entrapped, but perviousto gas and liquid and, in addition, radiation transmittable, and capableof supporting a matrix article, as indicated by reference numerals 26,26a and 26b containing substantially releasable semiochemical;

(5) At least one semiochemical-containing matrix 26, 26a, and 26bcomprising a porous containment agent containing in the intersticesthereof at least one semiochemical sustainably releasable therefrom,located on the upper surface of said macroporous mesh substance, 24;

(6) A sustainably vertically disposed drive shaft 43 supported forrotary motion about its axis 28c, extending from below and into thehollow interior of said inner hollow housing 37 along the sidelongitudinal dimension thereof;

(7) Motor means 35 connected to a first lower end of said drive shaft 43for rotating said drive shaft 43 about its axis 28c;

(8) Air flow creation means 36 attached to the second upper end of saiddrive shaft 43, being of such a design whereby the rotation of saiddrive shaft 43 directly causes the rotation of said air flow creationmeans 36 and induces the flow of air 34 from beneath said second innerhollow housing upwardly into the 3-space 52, 54 within said first hollowouter housing 28 between the outer side wall of the second inner hollowhousing 37 and the inner side wall 28b of said first outer hollowhousing 28;

(9) Radiation emission means 20 for emission of radiation 20r of aspecific wave length or of a range of wave lengths outwardly from theapparatus 100 located in the vicinity of the lower portion of saidsecond inner hollow housing 37, below the location of said 27;

(10) Radiation pulsing means 4201 connected via connections 4250 to saidradiation means 20 causing said raidation 20r to have a frequencyminicking insect wing beat and/or insect visual sensing frequencies;

(11) At least one power supply means 14, 16 associated with with saidtrap 100 energizing said radiation means 20, said radiation pulsingmeans 4201 and said motot means 35 on engagement of the power supply 14,16 with said motor means 35, said radiation pulsing means 4201 and saidradiation emission means 20

whereby arthropods 29b in the vicinity of said trap 100 are attracted bysaid pulsed radiation 20r to a location so close to said trap 100 thatin the event that an attracting chemical in said matrix 26, 26a, 26b isdetected by said arthropods 29b, said arthropods will enter the airstream 34 created by said air flow creation means 36 (or 50:50volume:volume air:CO₂ flow creation means 36), and be carried throughlocation 41 into the 3-space 52, 54 within said first hollow outerhousing 28 between the outer side wall 37a of said inner hollow housing37 and the inner side wall 28b of said first outer hollow housing 28.

Referring to the carbon dioxide flow, dry ice particles 69 or "chunks"is placed into zipper-locked bag 64 with zip-lock 67. The bag isconnected to tube 62, and tube 62 is mounted at mount 66 beneathcylinder 37 and the cylinder 12 which holds the power supply means 14,16, and motor means 35 together with radiation pulsing means 4201. Thezip-locked bags 64 is contained in insulated container 68. As soon asthe switch 18 is turned on in order to engage power supply means 14, 16with motor means 35 and radiation pulsing means 4201, a pinch clamp isremoved from tube 62 enabling carbon dioxide to flow through tube 62into the 3-space surrounding propeller 36 at location 41. The carbondioxide alone acts as an attractant for the species of insects:

(a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Culiseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.; and/or

(j) Lutzomyia spp.;

(k) Aedes spp.;

(1) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(p) Simuliidae spp.;

(q) Psorophora ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.).

If desired, the trap 100 may also or in the alternative to being placedin the ground through stake 42, suspended from suspension 30 held byclips 32.

The olfactometer illustrated in FIG. 2 and the olfactometer sectionillustrated in FIG. 2A are described in U.S. Pat. NO. 4,748,860 issuedon Jun. 7, 1988 the specification for which is incorporated herein byreference.

In FIG. 2, air source 734 feeds air through line 735 through airdistributors 736, 736a, et seq. onto base plate 717 containing insectlanding sites 710, 710a, et seq. The base plate 717 is separated fromthe spacer plate 729 for the air lines 736, 736a, et seq. whereby theair lines 736, 736a, et seq. are held in place at positions 731 and731a. Air exits through line 733a using exhaust fan 733. Theolfactometer is assisted with computer apparatus shown in schematic formand block flow diagram form using reference numerals 720, 721,723, 724and 739. Dampers 711a, 711b, et seq. hold base plate 717 in placehorizontally. When an insect lands on sensor landing site 710, 710a etseq. the landing is recorded electrically through a sensor shown inmagnified form in FIG. 14A. The sensor landing site includes atransducer 713 and causes an electrical impulse to proceed through wire718 and then through wire 719 to a multi-channel A-D converter 723(using electric power source 739) which is associated with program tapestorage 724, printer 720 and digital computer which is associated withmodem and main frame 721. Reference numeral 722 shows a "Faraday" cagecompleting the olfactometer circuit. The electical impulse thus effectsa recording of data as set forth in FIGS. 3A, 3B and 4A.

FIG. 2A is a detailed section showing one specific landing site 710a ofFIG. 2 on which the insect lands if attracted by one of the ester,alcohol and/or ether (e.g., the compound having the structure: ##STR38##containing compositions of our invention taken alone or in admixture ordoes not land if repelled by, for example, one or more of the ester,alcohol and/or ether compositions of our invention taken alone or inadmixture. At other landing sites nothing is located (and these are the"control" landing sites). At other sites a second repellent can belocated, or an attractant can be located. The olfactometer includes abase 781 on which the damper 711a, 71lb, et seq. are located namely base781. Base plate 717 is preferably covered with a film such as SARANWRAP® 725 so that any insects that are attracted to the landing sitesare not distracted to any other areas on base plate 717.

FIG. 3A and 3B are bar graphs of number of feeding contacts bymosquitoes (Aedes aegypti) on the "y" axis versus treatment composition(on the "x" axis) using the apparatus of FIG. 2. FIG. 3A sets forthmosquito contacts for a mean one hour feeding period. FIG. 3B sets forththe mosquito contact for a mean 2-6 hour contact period. The barindicated by reference numerals 301a and 301b are for clean air. Thebars indicated by reference numerals 302a and 302b are for diethylphthalate.

FIGS. 4A, 4B, 4C, 4D, 4E, 4F and 4G show repellency against house flies(Musca domestica L.(Diptera:Muscidae)) for FIG. 4A; horn flies(Haemotobia irritans (L.) for FIG. 4B; and mosquitoes (Aedes aegypti)for FIGS. 4C, 4D, 4E, 4F and 4G of INDISAN™ (the graphs indicated byreference numerals 404a, 404b, 404c, 404d, 404e, 404f and 404g. Thegraphs indicated by reference numerals 402a, 402b, 402c, 402d, 402e,402f and 402g show the attractiveness of air itself. The graphs areseries of graphs depicting in three dimensions (in a rectangular modefor the "x" and "y" axis) the repellency of INDISAN™ and the attractancyof air per se.

The graph of FIG. 4A shows repellency against house flies (Muscadomestica L.(Diptera:Muscidae)). The data supporting the graph of FIG.4A is set forth in Table I as follows:

                  TABLE I                                                         ______________________________________                                        MUSCA DOMESTICA L.(DIPTERA:MUSCIDAE)                                                   Ref-                                                                          erence                                                                        Numeral                                                              Composition                                                                            For      Insects Per Interval (10 Minute                             Tested   Graph    Intervals Totalling One Hour)                               ______________________________________                                        INDI-    404A     0     1    0    0    1    0    2                            SAN ™                                                                      Air      402A     0     0   466  376  288  206  173                           ______________________________________                                    

The data supporting the graph of FIG. 4B for horn flies (Haemotobiairritans (L.)) is set forth in Table II as follows:

                  TABLE II                                                        ______________________________________                                        (HAEMOTOBIA IRRITANS (L.)                                                             Ref-                                                                          erence                                                                Com-    Numeral                                                               position                                                                              For      Insects Per Interval (10 Minute                              Tested  Graph    Intervals Totalling One Hour)                                ______________________________________                                        INDI-   404B     0      42   7    9    4    2    11                           SAN ™                                                                      Air     402B     0     126  145  334  270  356  525                           ______________________________________                                    

FIG. 4C shows experiments run for a period of one hour with sixintervals of ten minutes each. The data supporting the graph of FIG. 4Care set forth in Table III as follows:

                  TABLE III                                                       ______________________________________                                        (AEDES AEGYPTI)                                                                       Ref-                                                                          erence                                                                Com-    Numeral                                                               position                                                                              For      Insects Per Interval (10 Minute                              Tested  Graph    Intervals Totalling One Hour)                                ______________________________________                                        INDI-   404C     0      9    12   15   11   9    2                            SAN ™                                                                      Air     402C     0     173  298  207  367  323  431                           ______________________________________                                    

The data supporting the graph of FIG. 4D is set forth in Table IV, formosquitoes. The graphs are based on experiments run for a period oftwelve hour with six intervals of two hours each. The data supportingthe graph of FIG. 4D is set forth in Table IV as follows:

                  TABLE IV                                                        ______________________________________                                        (AEDES AEGYPTI)                                                                          Reference Insects Per                                              Composition                                                                              Numeral   Interval (Two Hour Intervals                             Tested     For Graph Totalling Twelve Hours)                                  ______________________________________                                        INDISAN ™                                                                             404D      0     49   8   3   2   0  1                              Air        402D      0     82  95  82  12  99  5                              ______________________________________                                    

FIG. 4E shows repellency against mosquitoes (Aedes aegypti) by INDISAN™and attractiveness by air. The graphs are based on experiments run for aperiod of one hour with six intervals of ten minutes each. The datasupporting the graph of FIG. 4E is set forth in Table V as follows:

                  TABLE V                                                         ______________________________________                                        (AEDES AEGYPTI)                                                                        Ref-                                                                          erence                                                                        Numeral                                                              Composition                                                                            For      Insects Per Interval (Ten Minute                            Tested   Graph    Intervals Totalling One Hour)                               ______________________________________                                        INDI-    404E     0      5    3    0    0    0    6                           SAN ™                                                                      Air      402E     0     281  507  290  205  243  84                           ______________________________________                                    

FIG. 4F shows repellency of (Aedes aegypti) mosquitoes by INDISAN™ andattractiveness by air. The graphs are based on experiments run for aperiod of one hour with six intervals of ten minutes each. The datasupporting the graph of FIG. 4F is set forth in the following Table VI:

                  TABLE VI                                                        ______________________________________                                        (AEDES AEGYPTI)                                                                       Ref-                                                                          erence                                                                Com-    Numeral                                                               position                                                                              For      Insects Per Interval (Ten Minute                             Tested  Graph    Intervals Totalling One Hour)                                ______________________________________                                        INDI-   404F     0      0    0    0    0    0    0                            SAN ™                                                                      Air     402F     0     480  441  531  531  387  488                           ______________________________________                                    

FIG. 4G are graphs showing the repellency of (Aedes aegypti) by INDISAN™and attractiveness by air. The graphs are based on experiments run for aperiod of twelve hours with six intervals of two hours each. The datasupporting the graph of FIG. 4G is set forth in Table VII as follows:

                  TABLE VII                                                       ______________________________________                                        (AEDES AEGYPTI)                                                                        Reference                                                            Composition                                                                            Numeral   Insects Per Interval (Two Hour                             Tested   For Graph Intervals Totalling Twelve Hours)                          ______________________________________                                        INDI-    404G    0       1    0    0    0    0   0                            SAN ™                                                                      Air      402G    0     1616 1567 1466 1295 1211 502                           ______________________________________                                    

FIGS. 5A, 5B, 5C, 5D and 5E show relative repellencies againstmosquitoes (Aedes aegypti) of ORANGE FLOWER ETHER having the structure:##STR39## PAMPLEFLEUR® having the structure: ##STR40## VIOLIFF™ havingas its main constituent the compound having the structure: ##STR41## andin the case of FIG. 5B, 5C, 5D and 5E, geraniol coeur, as well as airper se. FIGS. 5A, 5B, 5C, 5D and 5E are series of graphs each depictingin three dimensions (in a rectangular mode for the "x" and "y" axes) therelative attractiveness or repellency of the ORANGE FLOWER ETHER,PAMPLEFLEUR®, VIOLIFF™ and geraniol coeur.

The graphs for FIG. 5A are based on experiments run for a period of onehour with six intervals of ten minutes each. The data supporting thegraph of FIG. 5A is set forth in Table VIII as follows:

                  TABLE VIII                                                      ______________________________________                                        (AEDES AEGYPTI)                                                                        Reference                                                            Composition                                                                            Numeral   Insects Per Interval (Two Hour                             Tested   For Graph Intervals Totalling Twelve Hours)                          ______________________________________                                        ORANGE   503A      0      1     0   0     1   0   0                           FLOWER                                                                        ETHER                                                                         PAMPLE   504A      0      0     0   0     0   0   0                           FLEUR ®                                                                   VIO-     505A      0      6     3   0     0   0   0                           LIFF ™                                                                     Air      502A      0     17    62  114   45  88  36                           ______________________________________                                    

Referring to FIG. 5B, the graphs are based on experiments run for aperiod of one hour with six intervals of ten minutes each. The datasupporting the graph of FIG. 5B is set forth in Table IX as follows:

                  TABLE IX                                                        ______________________________________                                        (AEDES AEGYPTI)                                                                        Reference                                                            Composition                                                                            Numeral   Insects Per Interval (Two Hopur                            Tested   For Graph Intervals Totalling Twelve Hours)                          ______________________________________                                        ORANGE   503B      0      5   0   2    6    5    11                           FLOWER                                                                        ETHER                                                                         PAMPLE   504B      0      1  48   38   4    56   8                            FLEUR ®                                                                   VIO-     505B      0      2   0   0    9    15   0                            LIFF ™                                                                     geraniol 506B      0      0   3   1    59   0    7                            coeur                                                                         Air      502B      0     10  65  121  491  267  248                           ______________________________________                                    

Referring to FIG. 5C, the graphs are based on experiments run for aperiod of six hours with six intervals of one hour each. The datasupporting the graph of FIG. 5C is set forth in Table X as follows:

                  TABLE X                                                         ______________________________________                                        (AEDES AEGYPTI)                                                                       Ref-                                                                          erence                                                                Com-    Numeral                                                               position                                                                              For      Insects Per Interval (Two Hour                               Tested  Graph    Intervals Totalling Twelve Hours)                            ______________________________________                                        ORANGE   503C    0      11   24   77   50  167  167                           FLOWER                                                                        ETHER                                                                         PAMPLE   504C    0      8    9    9    0    3    2                            FLEUR ®                                                                   VIO-     505C    0      0    6    0    3    1    5                            LIFF ™                                                                     geraniol 506C    0      7    3    10   7    2    0                            coeur                                                                         Air      502C    0     248  283  291  287  318  354                           ______________________________________                                    

Referring to FIG. 5D, the graphs are based on experiments run for aperiod of one hour with six intervals of ten minutes each. The datasupporting the graph of FIG. 5D is set forth in the following Table XI:

                  TABLE XI                                                        ______________________________________                                        (AEDES AEGYPTI)                                                                        Reference                                                            Composition                                                                            Numeral   Insects Per Interval (Two Hour                             Tested   For Graph Intervals Totalling Twelve Hours)                          ______________________________________                                        ORANGE   503D      0      7  32     5  15   1    0                            FLOWER                                                                        ETHER                                                                         PAMPLE   504D      0     10   0     3  25   3    0                            FLEUR ®                                                                   VIO-     505D      0      2   8     2   0   0    0                            LIFF ™                                                                     geraniol 506D      0      3   0     0   0   0    0                            coeur                                                                         Air      502D      0      2  30    53   6  329  277                           ______________________________________                                    

Referring to FIG. 5E, the graphs are based on experiments run for aperiod of six hours with six intervals of one hour each. The datasupporting the graph of FIG. 5E is set forth in Table XII as follows:

                  TABLE XII                                                       ______________________________________                                        (AEDES AEGYPTI)                                                                        Reference                                                            Composition                                                                            Numeral   Insects Per Interval (Two Hour                             Tested   For Graph Intervals Totalling Twelve Hours)                          ______________________________________                                        ORANGE   503E      0      0    1   1   20   22   60                           FLOWER                                                                        ETHER                                                                         PAMPLE   504E      0      0    3   0   0    0    0                            FLEUR ®                                                                   VIO-     505E      0      0    0   0   18   0    0                            LIFF ™                                                                     geraniol 506E      0      0    0   0   0    0    0                            coeur                                                                         Air      502E      0     277  31  94  109  259  169                           ______________________________________                                    

Regarding FIG. 6, FIG. 6 is a schematic cut-away elevation diagram of anextrusion and pelletizing apparatus useful for the fabrication of matrix26 used in carrying out a process of our invention. The operation of theapparatus causes an insect attractant or repellent to be incorporatedinto a polymer such as a polyethylene. Motor 215 drives the extruderscrews located at 223a in barrel 216a, the extruder being operated attemperatures in the range of from about 150° C. up to about 250° C. Atthe beginning of the barrel, resin at source 212 together withadditives, e.g., processing aides and densifiers at location 213 isadded via addition funnel 214 into the extruder. Simultaneously (whenthe operation reaches "steady state"), insect repellent, e.g., thePAMPLEFLEUR® having the structure: ##STR42## of our invention is addedto the extruder at one or more barrel segments, S-3, S-4, S-5, S-6, S-7and S-8 of the extruder (which may be a twin screw or single screwextruder) at locations 218a, 218b, 218c, and 218d (for example) by meansof gear pump 223 from source 217. From source 219 into barrel segementsS-5, S-6, S-7, S-8, S-9 and S-10, a gaseous liquid blowing agent, e.g.,nitrogen, carbon dioxide and the like are added simultaneously with theaddition of insect repellent, e.g., the PAMPLEFLEUR® of our invention.The feed rate range of resin is about 80-300 pounds per hour. The feedrate range of insect repellent is between 1% and 35% of the feed raterange of the resin. The blowing agent range is such that the pressure ofthe gas or the pressure over the liquid being fed into the extruder isbetween about 50 and 200 psig if, indeed, blowing agent is added. Ifdesired the extruded ribbon or cylinder may be passed through water bath220 and pelletizer 221 into collection apparatus 221a.

A preferred embodiment of our invention set forth in FIGS. 7-16comprises an ellipsodially shaped detergent tablet 830 containing asolid plastic core 832 which can be fabricated from, for example,polyethylene, polypropylene, nylon or any polymer capable of havingtherein microvoids from which insect repelling substance, e.g., thePAMPLEFLEUR® of our invention will be controllably transported from theplastic core into and through the soap cake over a reasonable period oftime during the use of the soap cake. Such soap cake can be used in awashing procedure by an individual as during a shower. Immediatelysubsequent to the shower and for a period of ten hours, insectrepellency will be had against house flies, mosquitoes and horn flieswhen using the esters, alcohols or ether of our invention. Such polymerscan be microporous polymers such as those described in U.S. Pat. No.4,247,498 issued on Jan. 27, 1981, the specification for which isincorporated hereby by reference. Surrounding the central plastic corecontaining insect repellent 832 as detergent 830 which is in the solidphase at ambient conditions, e.g., room temperature and atmosphericpressure. Examples of workable detergents 830 are "elastic" detergentssuch as those described in U.S. Pat. No. 4,181,632 issued on Jan. 1,1980, the disclosure of which is incorporated by reference herein, or"transparent" soaps such as those set forth in U.S. Pat. No. 4,165,293issued on Aug. 21, 1979, the disclosure of which is incorporated byreference herein. Other examples of the detergent 830 useful in ourinvention are those set forth as "variegated soaps" in Canadian LettersPatent No. 1,101,165 issued on May 19, 1981.

On use of the soap tablet 830 or detergent bar, the insect repellentagent, e.g., one or more of the esters, alcohols or ether of ourinvention originally located in plastic core 832 as transported at asteady state from core 832 through core surface 831 through thedetergent 830 and finally through the surface of the detergent bar at,for example, 833, 834,835 and 836.

The detergent bar or tablet 830 of our invention may be of any geometricshape, for example, a rectangular parallelpiped tablet as shown in FIGS.11, 12 and 13 containing solid plastic core 839. The insect repellentlocated in solid plastic core 839 on use of the detergent bar passesthrough at a steady state, surface 832 of FIG. 12, detergent 838 andfinally surface 839 at, for example, locations 840,841,842 and 843. Theenvironment surrounding the detergent bar on use thereof is then treatedwith insect repellent, e.g., PAMPLEFLEUR® or INDISAN™, at 843, 844 and845. Optionally, aromatizing agent (other than the alcohols, esters orether of our invention) can also be contained in the detergent bar andso the environment surrounding the detergent bar on use thereof (in awashing procedure by a person) would also be aesthetically aromatized at843,844 and 845, for example.

As shown in FIGS. 14, 15 and 16, the plastic core of the detergenttablet 830 may have a single finite void at its center 851 (of FIGS. 15and 16) in which the insect repellent agent and optionally thearomatizing agent is contained. The plastic core is a shell 848 havingouter surface 852 (shown in FIGS. 15 and 16). The insect repellent agent(and, optionally the additional aromatizing agent) contained in the voidin the plastic core permeates through shell 848, past surface 852 at asteady state through the detergent 847 and to the environment at, forexample, 856, 857, 858 and 859.

In addition to the insect repellent contained in the core, e.g., core839 or core void the core can also contain other materials, fortherapeutic use, for example, bacteriostats, deodorizing agents and thelike which are compatible with the insect repellents, the esters,alcohols and ether of our ivention, e.g., ORANGE FLOWER ETHER having thestructure: ##STR43## In the alternative, the plastic core of thedetergent tablet of FIGS. 14, 15 and 16 may have an empty single finitevoid at its center 851 with the insect repellent contained in the shell848.

At the end of the use of the detergent tablet, the hollow core or thesolid core can be used as an insect repelling and aroma imparting airfreshener household article. In addition, depending on the ratio of thevolume of the void 851, to the solid part of the detergent tablet ofFIGS. 14, 15 and 16, the detergent tablet of FIGS. 14, 15 and 16 can beso fabricated that it will float on the surface of the liquid in whichit is being used and this physical attribute has certain obviousadvantages.

FIGS. 17, 18, 19 and 20 are bar graphs setting forth the relativeattractancy or repellency of certain compositions when tested in thefield olfactometer of our invention of FIG. 1. The "x" axis of each ofthe graphs sets forth the mean number of mosquitoes, to wit:

(a') Aedes aegypti;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian

trapped. The "x" axis sets forth the treatment composition.

Referring to FIG. 17, the bar indicated by reference numeral 1700 showsattractancy by a 50:50 mixture of air and CO₂ with a feed rate of CO₂being 2.71 gram moles per hour. The bar indicated by reference numeral1702 is for VIOLIFF™. The bar indicated by reference numeral 1704 is forPAMPLEFLEUR®.

The apparatus of FIG. 1 has six infrared light emitting diodes.

Referring to FIG. 18, the bar indicated by reference numeral 1800 is fora 50:50 l mole:mole mixture of air and CO₂ with a feed rate of CO₂ being2.71 gram moles per hour. The bar indicated by reference numeral 1802 isfor INDISAN™.

The apparatus used for the purposes of creation of the data for FIG. 18,the apparatus of FIG. 1 has three infrared light emitting diodes.

Referring t o FIG. 19, the bar indicated by reference numeral 1900 isfor a 50:50 mole:mole mixture of air and CO₂ with the feed r ate of CO₂being 2.71 gram moles per hour. The bar indicated by reference numeral1902 is for VIOLIFF™. This graphs shows that VIOLIFF™ is a repellent forthe species:

(a') Aedes aegypti;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian

and the mixture of CO₂ and air is an attractant for the insect species:

(a') Aedes aegypti;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian.

The apparatus of FIG. 1 for the purposes of creation of the data forFIG. 19 has infrared light emitting diodes.

With respect to FIG. 20, the bar indicated by reference numeral 2000 isfor a 50:50 mole:mole mixture of air and CO₂ with a feed rate of CO₂being 2.71 gram moles per hour. The bar indicated by reference numeral2002 is for PAMPLEFLEUR®. The bar indicated by reference numeral 2004 isfor geraniol. The apparatus of FIG. 1 for the purposes of creation ofthe data for FIG. 20 has twelve infrared light emitting diodes. The datashows that the mixture of air and CO₂ is an attractant for the insectspecies:

(a') Aedes aegypti;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian

and is a repellent for PAMPLEFLEUR® and geraniol coeur with respect tothe insect species:

(a') Aedes aegypti;

(b') Aedes albopictus;

(c') Anopheles spp.;

(d') Culex spp.;

(e') Aedes spp.;

(f') Culex nigripalpus;

(g') Aedes atlanticus;

(h') Culex salinarius;

(i') Aedes vexans;

(j') Aedes infirmatus; and

(k') Anopheles crucian.

FIG. 21 is the GLC profile for the reaction product prior todistillation of Example V. Reference numeral "1" represents the peak formethyl alcohol. Reference numeral "2" represents the peak for4-cyclooctenyl formate that is not reacted. Reference numeral "3"represents the peak for 4-cyclooctenyl methyl carbonate having thestructure: ##STR44##

The following examples set forth processes for carrying out ourinvention by means of repelling certain species of insects from threedimensional spaces inhabitable by such insects. The examples are notintended to be limiting and the invention is only to be limited by theclaims. Unless otherwise indicated all parts and percentages are byweight.

EXAMPLE I Paraffin Wax Candle Body

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Paraffin wax          95.0                                                    PAMPLEFLEUR ® having                                                                            3.0                                                     the structure:                                                                 ##STR45##                                                                    ORANGE FLOWER ETHER   2.0                                                     having the structure:                                                          ##STR46##                                                                    ______________________________________                                    

The paraffin wax is intimately admixed at 150° C. and 10 atmospherespressure with the ORANGE FLOWER ETHER and PAMPLEFLEUR® in an autoclavewith intensive shaking. The autoclave pressure is maintained with anitrogen atmosphere. At the end of the period of one hour the autoclaveis depressurized, the autoclave is opened and the resulting mixture ispoured into cylindrical candle molds containing wicks.

The resulting candles on use evolve an aesthetically pleasing aroma and,in addition, give rise to efficacious house fly repellency. The candlesare effective in preventing house flies from entering a room in whichone candle is burning for a period of 10 minutes, the said room havingdimensions of 6'×15'×15' having a 3'×3' open portal adjacent to a housefly-infested region in the month of August in Highlands, N.J., next to avery swampy area.

EXAMPLE II

A transparent candle base is produced by intimately admixing thefollowing ingredients:

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        VERSAMID ® 1635                                                                            34.0                                                         Barlol 12C2      51.0                                                         Butyl Stearate    3.5                                                         NEVEX ® 100   5.0                                                         SPAN ® 60     1.5                                                         Isopropyl Isostearate                                                                           4.0                                                         Isopropyl Myristate                                                                             4.0.                                                        ______________________________________                                    

The foregoing mixture is placed in an autoclave and intimately admixedwith a perfume-scent repellent composition containing VIOLIFF™ preparedaccording to the process of Example V, infra and containing a majorproportion of the compound having the structure: ##STR47## and a minorproportion of the compound having the structure: ##STR48## The VIOLIFF™is incorporated at the rate of 8% by weight of the total candle basecomposition.

The autoclave is sealed and heated to 180° C. under 15 atmospherespressure and maintained with vigorous shaking for a period of fivehours. At the end of the five hour period, the autoclave isdepressurized (being under a nitrogen pressure atmosphere) and theautocalve is opened and the contents are then poured into cylindricalcandle molds 4" in height and 2" in diameter containing 0.125' wicks.The resulting candles have efficacious insect repellencies and haveaesthetically pleasing aromas on use.

The candles are effective in preventing the following insects:

(a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Culiseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.; and/or

(j) Lutzomyia spp.;

(k) Aedes spp.;

(1) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(p) Simuliidae spp.;

(q) Psorophora ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.)

from entering a room in which two candles have been burning for 15minutes. The said room having dimensions of 6'×15'×15' and having a3'×3' open portal adjacent a house fly, horn fly and mosquito infestedregion in Highlands, N.J., in the month of August in the temperate zone.

EXAMPLE III

The following candle base composition of matter is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Polyamide (VERSAMID ® 940                                                                        30.0                                                   manufactured by the Henkel                                                    Chemical Corporation of                                                       Minneapolis, Minnesota)                                                       Stearic acid            5.0                                                   Methyl-12-hydroxy stearate                                                                            5.0                                                   10 Carbon primary alcohol                                                                             5.0                                                   manufactured by the (Continental Oil                                          Company); ALFOL ® 10);                                                    (ALFOL ® is a trademark of Conoco                                         Division of E. I. DuPont of                                                   Wilmington, Delaware                                                          Myristyl Myristate     10.0                                                   Stearic hydrazide       0.1                                                   Diethyl phthalate       2.0                                                   INDISAN ™            3.0                                                   Light White Mineral Oil                                                                              q.s. to 100%                                           ______________________________________                                    

All of the materials except the polyamide are mixed at room temperature.The mixture is then heated gradually with gradual addition of thepolyamide and with agitation beginning with the commencement of additionof the polyamide. In the proportion required, the polyamide does notbecome fully soluble until the mixture reaches the temperature of about220° F. The temperature on the order of 220° F. to 230° F. is maintainedat atmospheric pressure with continued agitation until the polyamide isfulloy dissolved. Since higher temperatures promote solution of thepolyamide this temperature range can be slightly exceeded with someadvantage. As soon as the polyamide has dissolved completely, themixture is poured into molds following the conventional practice in themanufacture of molded candles. As the candles cool they harden. Thecandles are then freed from the molds and tested for insect repellency.

The candles are effective in preventing the following insects fromentering a room in which two candles have been burning for 15 minutes,the said room having dimensions of 6'×15'×15' and having a 3'×3' openportal adjacent to an insect infested region in the month of August inHighlands, N.J.:

(a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Culiseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.; and/or

(j) Lutzomyia spp.;

(k) Aedes spp.;

(l) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(p) Simuliidae spp.;

(q) Psorophora ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.).

EXAMPLE IV

A study was conducted to evaluate the efficacy of candles which aredesignated "A", "B" and "C" in repelling house flies (Musca domesticaL.(Diptera:Muscidae)).

Candle "A" contained 95% Paraffin Wax and 5% of the followingcomposition:

100 Parts by weight of VIOLIFF™; and

700 Parts by weight of a perfume composition containing the followingingredients:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        (i)   Perfume mixture of essential                                                                       83.8                                                     grams oils and chemicals, to with                                             the methyl ester of 2,5-dihydroxy-                                            4-6-dimethyl benzoic acid; dihydro                                            myrcenol; oakmoss absolute; benzyl                                            acetate; geraniol; isobornyl acetate;                                         citronellyl acetate; para-t-butyl                                             phenyl isovaleraldehyde; benzyl                                               slicylate; hexyl cinnamic aldehyde;                                           geranonitrile; patchouli oil;                                                 alpha-terpineol; tetrahydromugol;                                             phenyl ethyl alcohol; cedrenal;                                               methyl ionone; cinnamyl acetate;                                              benzyl benzoate                                                         (ii)  Solvent: the methyl ester of                                                                        4.00                                                    dihydroabietic acid                                                     ______________________________________                                    

Candle "B" contained 90% Paraffin Wax and 10% citronella oil.

Candle "C" contained only Paraffin Wax.

The candles are allowed to burn for 20 minutes and the number of houseflies repelled from a house fly-infested room is recorded for the next60 minutes with the following equipment and procedure:

MATERIALS Test Chamber

The evaluation was conducted in a 28.3 cubic meter chamber with airingports. A screened cage measuring 15 xm×15 cm=47.5 cm was attached insidean upper airing port, and a screened repellency observation cagemeasuring 15 cm ×15 cm ×32.5 cm was attached outside the upper airingport. The two cages were held together by a Masonite plate which fitfirmly in the airing port. A 4-cm hole located in the center of eachMasonite plate provided an escape for the test insects. A barrier wasused to close the hole.

Attractant

A caged mouse was used as an attractant and was placed inside thechamber in the larger section of the repellency cage.

Test Insect

Adult house flies (Musca domestica) are test insects.

Procedure

For each replicate, 75 to 100 adult house flies were removed from therearing cage by means of a vacuum aspirator, and transferred by carbondioxide anesthesia to the inner cage containing the mouse. The assembledcage was placed in one of the upper ventilation ports of the chamber.

For each experimental situation the test insects were transferred to aclean cage containing the mouse. A house fly candle was placed centrallyon the chamber floor and burned for 20 minutes before initiating therepellency counts. The maximum period for the repellency counts was 60minutes. The first repellency count was made at 10 minutes after theburning ended, and subsequent counts were taken at 5-minute intervalsthereafter. The number of house flies repelled were those escaping tothe outside cage. For the control counts were made in a similar manner,but no candle was burned.

The same three candles were used for all four relicates. Betweenreplicates the chamber was exhausted, the Kraft paper flooring for thechamber was replaced, and the two screened repellency cages weresubmerged in hot detergent water, rinsed and dried.

Results

The average percent of house flies repelled for each 5-minute exposureperiod through 60 minutes is reported in the following Table XIII:

                                      TABLE XIII                                  __________________________________________________________________________    House Flies Repelled At Five Minute Time Intervals                            20 Minutes Post Exposure                                                                          Cumulative Number of                                                    Number of                                                                           House Flies Repelled at Indicated Minutes                                                           Overall                             SAMPLE:  Replicate                                                                          House Flies                                                                         10                                                                              15                                                                              20                                                                              25                                                                              30                                                                              35                                                                              40                                                                              45                                                                              50                                                                              55                                                                              60                                                                              Percent                             __________________________________________________________________________    Untreated                                                                              1     93   1 1 1 1 1 2 2 3 3 4 6  6.45                               (no candle                                                                             2     67   0 1 2 3 5 6 6 6 6 7 7 10.45                               used)    3     86   2 2 2 3 4 6 6 7 7 7 7  8.14                                        4     90   2 3 3 3 3 4 5 5 5 5 5  5.56                               Total         336   5 7 8 10                                                                              13                                                                              17                                                                              19                                                                              21                                                                              21                                                                              23                                                                              25                                    Average Percent     1 2 2  3                                                                               4                                                                               5                                                                               6                                                                               6                                                                               6                                                                               7                                                                               7                                                                               7.44                               A        1    108   2  5                                                                               7                                                                               8                                                                               8                                                                               8                                                                               8                                                                              10                                                                              10                                                                              10                                                                              12                                                                              11.11                                        2     95   0  5                                                                               5                                                                               6                                                                               7                                                                               7                                                                               9                                                                              11                                                                              12                                                                              12                                                                              16                                                                              16.84                                        3     86   3  6                                                                               8                                                                               8                                                                              10                                                                              10                                                                              11                                                                              11                                                                              12                                                                              12                                                                              13                                                                              15.12                                        4     96   2  3                                                                               5                                                                               6                                                                               9                                                                              11                                                                              11                                                                              14                                                                              16                                                                              17                                                                              17                                                                              17.71                               Total         385   7 19                                                                              25                                                                              28                                                                              34                                                                              36                                                                              39                                                                              46                                                                              50                                                                              51                                                                              58                                    Average Percent     2  5                                                                               6                                                                               7                                                                               9                                                                               9                                                                              10                                                                              12                                                                              13                                                                              13                                                                              15                                                                              15.06                               B        1     80    4                                                                               5                                                                               7                                                                               7                                                                               8                                                                               8                                                                               9                                                                               9                                                                               9                                                                              10                                                                              11                                                                              13.75                                        2    100    2                                                                               4                                                                               5                                                                               6                                                                               7                                                                              10                                                                              11                                                                              11                                                                              11                                                                              12                                                                              12                                                                              12.00                                        3     87    2                                                                               2                                                                               3                                                                               4                                                                               5                                                                               5                                                                               6                                                                               6                                                                               6                                                                               6                                                                               7                                                                               8.04                                        4     91    2                                                                               4                                                                               5                                                                               6                                                                               6                                                                               6                                                                               7                                                                               7                                                                               7                                                                               9                                                                              10                                                                              10.99                               Total         358   10                                                                              15                                                                              20                                                                              23                                                                              26                                                                              29                                                                              33                                                                              33                                                                              33                                                                              37                                                                              41                                    Average Percent      3                                                                               4                                                                               6                                                                               6                                                                               7                                                                               8                                                                               9                                                                               9                                                                               9                                                                              10                                                                              10                                                                              11.45                               C        1     79    6                                                                               8                                                                               8                                                                               8                                                                               8                                                                               8                                                                               8                                                                               8                                                                               8                                                                               9                                                                              10                                                                              12.66                                        2     86    3                                                                               5                                                                               5                                                                               6                                                                               6                                                                               6                                                                               6                                                                               6                                                                               7                                                                               7                                                                               8                                                                               9.30                                        3     92    2                                                                               4                                                                               4                                                                               5                                                                               7                                                                               7                                                                               7                                                                               7                                                                               7                                                                               7                                                                               8                                                                               8.70                                        4     91    0                                                                               1                                                                               1                                                                               2                                                                               2                                                                               2                                                                               4                                                                               6                                                                               7                                                                               7                                                                               9                                                                               9.89                               Total         348   11                                                                              18                                                                              18                                                                              11                                                                              23                                                                              23                                                                              25                                                                              27                                                                              29                                                                              30                                                                              35                                    Average Percent      3                                                                               5                                                                               5                                                                               6                                                                               7                                                                               7                                                                               7                                                                               8                                                                               8                                                                               9                                                                              10                                                                              10.06                               __________________________________________________________________________

The results of this experiment show that the candle containing theVIOLIFF™ composition (2.5% of the total weight) is about 40% moreefficacious from an insect repellency standpoint than a candlecontaining 10% citronella oil . . . and in addition, such candlescontaining the VIOLIFF™ composition on burning yield an aestheticallypleasing scent which is totally unlike the 10% citronella oil containingcandle which yields an aesthetically displeasing scent.

EXAMPLE II Preparation of Composition Containing Major Proportion of4-Cyclooctenyl Methyl Carbonate (VIOLIFF™)

Into a 5-liter reaction flask equipped with heating mantle, stirrer,Bidwell trap, addition funnel, thermometer, reflux condenser andnitrogen blanket apparatus, are placed 2 liters (22.0 moles) of dimethylcarbonate and 81 grams (1.5 moles) of powdered sodium methoxide. Theresulting mixture is heated to 65° C. and over a period of 4 hours whilemaintaining the temperature of the mixture at 60°-65° C., 1,719 grams(11.0 moles) of the composition containing a preponderance of4-cyclooctenyl formate produced according to Example I (bulkeddistillation Fractions 5, 7 and 9) of U.S. Pat. No. 4,452,730 issued onJun. 5, 1984 is added to the reaction mass while recovering methylformate reaction product via the Bidwell trap. After additgion iscomplete, the reaction mass is heated to 70° C. in order to remove theremaining the reamining formate reaction product.

The reaction mass is then washed with two 500 ml portions of saturatedsodium chloride and distilled on a 1" Goodloe column yielding thefollowing fractions:

    ______________________________________                                                                          % of 4-                                     Frac-                 Pres-       cyclo-  Weight                              tion  Vapor   Liquid  sure        octenyl of                                  Num-  Temp.   Temp.   mm/   Reflux                                                                              Methyl  Fraction                            ber   (°C.)                                                                          (°C.)                                                                          Hg.   Ratio Carbonate                                                                             (grams)                             ______________________________________                                         1    48/64   85/95   1.8/3.0                                                                             4:1   --      --                                   2    62       97     1.4   4:1   --      --                                   3    70      100     2.6   4:1   --      --                                   4    77      100     1.4   4:1   --      --                                   5    72/87   95/98   2.3   9:1   78.0    --                                   6    9-02    112/    6.5   4:1   93.0     52                                               105                                                              7    92      107     4.6   4:1   97.0     88                                  8    92      107     4.0   4:1   --      112                                  9    86      110     3.0   4:1   98.0    119                                 10    86      113     3.0   4:1   --      113                                 11    86      115     3.0   4:1   98.8    130                                 12    86      116     3.0   4:1   --       55                                 13    86      118     3.0   4:1   99.8    101                                 14    86      120     3.0   4:1   --       65.                                ______________________________________                                    

Fractions 7-14 are bulked for the purpose of organoleptic evaluation.

FIG. 21 is the GLC profile for the reaction product prior todistillation. The numeral "1" represents the peak for methyl alcohol.The numeral "2" represents the peak for 4-cyclooctenyl formate that isnot reacted. The reference numeral "3" represents the peak for the4-cyclooctenyl methyl carbonate reaction product having the structure:##STR49##

FIG. 22 is the GLC profile for Fraction 13 of the foregoing distillationcontaining a major proportion of the compound having the structure:##STR50## as well as a minor proportion of the compound having thestructure: ##STR51##

FIG. 23 is the NMR spectrum for Fraction 13 of the foregoingdistillation containing a major proportion of the compound having hestructure: ##STR52## as well as a minor proportion of the compoundhaving the structure: ##STR53## (Solvent: CFCl₃ ; Field Strength: 100MHz).

FIG. 24 is the infrared spectrum for Fraction 13 of the foregoingdistillation containing a major proportion of the compound having thestructure: ##STR54## as well as a minor proportion of the compoundhaving the structure: ##STR55##

FIG. 25 is the GLC profile for Fraction 7 of the foregoing distillationcontaining a major proportion of the compound having the structure:##STR56## and a minor proportion of the compound having the structure:##STR57## (ratio of compound having the structure: ##STR58## to compoundhaving the structure: ##STR59## is 77:19).

FIG. 26 is the NMR spectrum for Fraction 7 of the foregoing distillationcontaining the compound having the structure: ##STR60## in majorproportion and the compound having the structure: ##STR61## in minorproportion (Solvent: CFCl₃ ; Field Strength: 100 MHz ).

FIG. 27 is the infrared spectrum for Fraction 7 of the foregoingdistillation containing a major proportion of the compound having thestructure: ##STR62## and a minor proportion of the compound having thestructure: ##STR63##

Bulked distillation Fractions 7-14 have a fruity (pear, banana), sweet,violet-like, green and cucumber aroma profile. In addition bulkedFractions 7-14 have the ability to repel each of the species of thefollowing insects:

(a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Cullseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.; and/or

(j) Lutzomyia spp.;

(k) Aedes spp.;

(1) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(P) Simuliidae spp.;

(q) Psorophora ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.).

EXAMPLE VI Preparation of Meta (Iso-Camphyl-5-Cyclohexanol STAGE 1

Into a 1 liter autoclave is placed the following materials:

    ______________________________________                                        Reaction product of    397 grams                                              catehol and camphene                                                          produced according to                                                         Example XI (Fractions 3-13)                                                   of U.S. Letters Patent                                                        No. 4,014,944 issued on                                                       March 27, 1977, the                                                           specification for which                                                       is incorporated by reference                                                  herein                                                                        Isopropyl alcohol      100 ml                                                 Raney Nickel            30 grams.                                             ______________________________________                                    

After sealing, the autoclave is then purged with nitrogen followed byhydrogen. The autoclave is pressurized with hydrogen to 500 psig andheated to 100° C., at which temperature stirring is commenced. Theautoclave is then heated up to a temperature of less than 160° C. forthe major portion of the time of the 1st stage of hydrogenation.However, as the uptake of hydrogen diminishes, the autoclave is heatedto a temperature of 205° C. A table showing the time, temperature ofhydrogenation, autoclave pressure, reservoir pressure, pressure drop andtotal pressure drop is set forth below:

    ______________________________________                                                                                Total                                                 Auto-    Reservoir                                                                             Pressure                                                                             Pressure                                   Temperature                                                                              clave    Pressure                                                                              Drop   Drop                                  Time (°C.)                                                                             (psig)   (psig)  (psig) (psig)                                ______________________________________                                        0920  75        500      2010    --     --                                    0947 110        540      2010    --     --                                    0952 125        340      2010    --     --                                    1017 110        500       850    1160   1160                                  1030 125        500       580     170   1430                                  1030 125        500      2010    --     --                                    1045 145        --               --     --                                    1055 180        500       600    1410   2840                                  1055 180        480      2010    --     --                                    1205 160        500       680    1330   4170                                  1205 160        480      2000    --     --                                    1240 170        480      1620     380   4550                                  1317 195        480      1430    --     --                                    1533 205        500      1130    --     --                                    1616 205        480      1120     500   5050                                  1920  90        150      --      --      --.                                  ______________________________________                                    

At the end of the period of 10 hours as is set forth in the above table,the autoclave is opened and the reaction mass is filtered. The autoclaveis then rinsed twice with isopropyl alcohol. The solvent is stripped offat 110° C. and atmospheric pressure, then at 25 mm/Hg. at 11° C. At thispoint IR and GLC analysis indicates that the reaction mass is a mixtureof compounds having the structure: ##STR64##

STAGE 2

The solvent-stripped reaction product of the first stage ofhydrogenation is admixed with 30 grams of Raney nickel and 100 grams ofisopropyl alcohol and replaced into the 1 liter autoclave. Aftersealing, the autoclave is purged with nitrogen followed by hydrogen. Theautoclave is then heated to 217° C. and held at 225°-230° C. and 500psig for a period of eight hours. At the end of the eight hour period,the reaction mixture is cooled, the autoclave is opened and the reactionmass is removed from the autoclave, filtered and the isopropanolrecovered at atmospheric pressure at 100° C., then at 25 mm/Hg. at 110°C. 19.5 Grams of Primol is added to the resulting oil which is thendistilled on a 6" vigreaux column yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid      Vacuum Weight                                    Fraction Temp.   Temp.       mm/Hg. of                                        No.      (°C.)                                                                          (°C.)                                                                              Pressure                                                                             Fraction                                  ______________________________________                                         1       113     148         2.3     4.9                                       2       146     165         3.5    17.4                                       3       139     165         2.7    12.4                                       4       145     170         2.7    11.6                                       5       147     175         2.7    14.0                                       6       154     175         2.7    15.5                                       7       158     178         2.7    16.7                                       8       165     178         2.5    22.7                                       9       165     185         2.8    15.8                                      10       156     183         2.4    21.4                                      11       162     187         2.4    22.1                                      12       172     192         2.4    26.0                                      13       187     204         2.3    18.2                                      14       209     236         2.5    21.9                                      15       235     250         2.7    20.5                                      16       241     250         2.7     8.6                                      ______________________________________                                    

Fractions 6-14 are bulked and the resulting product has a strongsandalwood aroma with woody nuances.

The resulting product is a mixture of several chemical compoundscontaining in a major proportion the compound having the structure:##STR65## The GLC profile thereof is set forth in FIG. 29. The resultingmaterial has the ability to repel the following species of insects froma three dimensional space inhabitable by such insects:

(a) Musca domestica L.(Diptera:Muscidae);

(b) Aedes aegypti;

(c) Aedes albopictus;

(d) Anopheles spp.;

(e) Coquillettidia perturbans;

(f) Culiseta spp.;

(g) Culex spp.;

(h) Psorophora spp.;

(i) Culicoides spp.; and/or

(j) Lutzomyia spp.;

(k) Aedes spp.;

(1) Culex nigripalpus;

(m) Aedes atlanticus;

(n) Culex salinarius;

(o) Aedes vexans;

(p) Simuliidae spp.;

(q) Psorophora ferox;

(r) Aedes infirmatus;

(s) Drosophila melanogaster;

(t) Coccinellidae;

(u) Anopheles crucian;

(v) Psorophora columbiae; and

(w) Haemotobia irritans (L.).

What is claimed is:
 1. A method of repelling at least one of the insectspecies:(a) Musca domestica L.(Diptera:Muscidae); (b) Aedes aegypti; (c)Aedes albopictus; (d) Anopheles spp.; (e) Coquillettidia perturbans; (f)Cullseta spp.; (g) Culex spp.; (h) Psorophora spp.; (i) Culicoides spp.;and/or (j) Lutzomyia spp.; (k) Aedes spp.; (l) Culex nigripalpus; (m)Aedes atlanticus; (n) Culex salinarius; (o) Aedes vexans; (p) Simuliidaespp.; (q) Psorophora ferox; (r) Aedes infirmatus; (s) Drosophilamelanogaster; (t) Coccinellidae; (u) Anopheles crucian; (v) Psorophoracolumbiae; and (w) Haemotobia irritans (L.)for a finite period of timefrom a three dimensional space inhabitable by said insect speciescomprising the step of exposing said three dimensional space to aneffective: (a) Musca domestica L.(Diptera:Muscidae); (b) Aedes aegypti;(c) Aedes albopictus; (d) Anopheles spp.; (e) Coquillettidia perturbans;(f) Culiseta spp.; (g) Culex spp.; (h) Psorophora spp.; (i) Culicoidesspp.; and/or (j) Lutzomyia spp.; (k) Aedes spp.; (1) Culex nigripalpus;(m) Aedes atlanticus; (n) Culex salinarius; (o) Aedes vexans; (p)Simuliidae spp.; (q) Psorophora ferox; (r) Aedes infirmatus; (s)Drosophila melanogaster; (t) Coccinellidae; (u) Anopheles crucian; (v)Psorophora columbiae; and (w) Haemotobia irritans (L.) repellingconcentration and quantity of at least one composition of matterselected from the group consisting of:(i)2,4-dimethyl-4-phenyl-1-butanol having the structure: ##STR66## and (ii)an ether having the structure: ##STR67##
 2. The process of claim 1wherein the three dimensional space is exposed to2,4-dimethyl-4-phenyl-1-butanol having the structure: ##STR68##
 3. Theprocess of claim 1 wherein the three dimensional space is exposed to anether having the structure: ##STR69##
 4. A process for repelling bloodfeeding arthropods from a person consisting of the steps of:(i)fabricating an insect repelling soap comprising a soap base and inintimate contact therewith an alcohol or ether containing composition ofmatter which is selected from the group consisting of:(a)2,4-dimethyl-4-Phenyl-1-butanol having the structure: ##STR70## and (b)an ether having the structure: ##STR71## and (ii) applying an effectiveamount of the thus fabricated soap to said person.